Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/003—Phosphorus
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B25/00—Phosphorus; Compounds thereof
  • C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
  • C01G23/047—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G25/00—Compounds of zirconium
  • C01G25/02—Oxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

• This invention relates to a method of treating a titanium or zirconium salt of a phosphorus oxyacid, and more specifically, it relates to a method of separating a titanium or zirconium salt of a phosphorus oxyacid into phosphorus and an oxide of titanium or zirconium.
• these methods are defective in that the phosphoric acid component is recovered in the form of an alkali metal or alkaline earth metal phosphate of a small utility value.
• the former method is further defective in that in order to obtain titanium oxide or zirconium oxide which is useful as pigment it is necessary to oxidize the once recovered titanium tetrahalide or zirconium tetrahalide with the use of oxygen.
• the primary object of the present invention is to provide a method of treating a titanium or zirconium salt of t a phosphorus oxyacid which makes it possible to separate from the titanium or zirconium salt of a phosphorus oxyacid the titanium or zirconium component and the phosphorus oxyacid component in the most industrially advantageous forms.
• Another object of the present invention is to provide a method of treating a titanium or zirconium salt of a phosphorus oxyacid which makes it possible to recover the phosphorus oxyacid component in the form ofphosphorus.
• Still another object of the present invention is to provide a method of treating a titanium or zirconium salt of a phosphorus oxyacid which makes it possible to recover the titanium or zirconium in the form ofa metal or an oxide.
• Still another objectof the present invention is to provide a method of preparing an oxide of titanium or zirconium excellent in whiteness and hiding power from a titanium or zirconium salt ofa phosphorus oxyacid.
• Still another object of the present invention is to provide a method in which a titanium or zirconium salt ofa phosphorus oxyacid whose purification can be easily operated is selected as the starting material containing the titanium or zirconium component and the phosphorus oxyacid component, and in which by heating the above starting material in the presence of carbon or carbon monoxide, there can be obtained pure phosphorus and an oxide of titanium or zirconium substantially free from metallic impurities and from the phosphorus oxyacid component bonded thereto.
• a method of treating a titanium or zirconium salt of a phosphorus oxyacid which comprises heating a mixture of carbon and a titanium or zirconium salt of a phosphorus oxyacid in a nonoxidizing atmosphere at a temperature exceeding 900 C. or heating the titanium or zirconium salt of a phosphorus oxyacid in the absence of carbon in a carbon monoxide atmosphere at a temperature exceeding 900 C., thereby separating the phosphorus oxyacid component in the form of phosphorus vapor and recovering the titanium or zirconium component as solid residue.
• a titanium or zirconium salts of phosphorus oxyacids are used as starting material for titanium or zirconium.
• Such salts are known substances and in the present invention, any of titanium or zirconium salts of orthophosphoric acid or a water-soluble salt thereof to a sulfuric acid solution of titanium (see, for instance, the specification of British Pat. No. 261,051) and that zirconium phosphate can be obtained by adding phosphoric acid to a zirconium salt solution.
• a titanium salt of a phosphorus oxyacid to be used in the present invention can be generally prepared with ease by reacting an inorganic or organic acid solution of a titanium compound, a titanium salt per se or amorphous titanium oxide with a phosphorus oxyacid or a derivative thereof in the presence of water.
• a zirconium salt of a phosphorus oxyacid can be prepared with ease by reacting an inorganic or organic acid solution of a zirconium compound or a zirconium salt per se with a phosphorus oxyacid or a derivative thereof in the presence of water.
• any of phosphorus oxyacids can be used in this invention.
• orthophosphoric acid H PO metaphosphoric acid
• HOP pyrophosphoric acid H P O hexametaphosphoric acid [(HPO tripolyphosphoric acid rnr o phosphorous acid mp0, and hypophosphorous acid (H PO are used.
• derivatives of phosphorus oxyacids such as anhydrides (for instance, phosphorus pentaoxide), halides, oxyhalides, and salts of an alkali metal, an alkaline earth metal, ammonium, zinc and aluminum.
• the atomic ratio of titanium or zirconium to phosphorus may be within a broad range.
• the titanium or zirconium metallic component in the phosphorus oxyacid salt is expressed as M0 and the phosphorus oxyacid component as P 0 P 0 is containedin an amount of ranging from 0.01 to 3 moles, especially from 0.1 to 2 moles per mole of M0 ln case the phosphorus oxyacid component is present in an extremely large amount within the above range, it does not give any substantial advantage to the recovery of the titanium or zirconium component, and only phosphorus can be recovered in a great amount as the phosphorus oxyacid component, resulting in no other economical advantage.
• the titanium or zirconium salt of a phosphorus oxyacid cannot be obtained in the form of a gel and it sometimes becomes difficult to agglomerate the titanium or zirconium salt of a phosphorus oxyacid and remove metallic impurities therefrom by extraction, with the consequence that it becomes impossible to use a titanium or zirconium salt of a phosphorus oxyacid of a high purity. Accordingly, it is especially preferred in the present invention that the content of the phosphorus oxyacid component, expressed in terms of the M0 P 0 mole ratio, is within a range of] l.5-0.l.
• An optional titanium salt of a phosphorus oxyacid may be used in the present invention, but, as mentioned above, it is especially preferable to use a gel of a titanium salt of a phosphorus oxyacid prepared by a method which comprises forming a liquid mixture composed mainly of a titanium salt of a phosphorus oxyacid, molding it into a gel of small masses and extracting metallic impurities from said gel of small masses.
• a titanium salt of a phosphorus oxyacid substantially free from metallic impurities such as Fe, Mo, V, Cr, F and As from titanium-containing ores such as ilmenite, iron sand slag, rutile and high-titanium, slag, with the use of such starting phosphorus oxyacid as crude phosphoric acid and purified phosphate rock. Accordingly, since a titanium salt of a phosphorus oxyacid prepared by the above method can give high-purity phosphorus and metallic titanium or titanium oxide which need not be purified by after-treatments, the use of the titanium salt of a phosphoric oxyacid prepared by the above mentioned method is particularly preferred.
• a gel of a zirconium salt of a phosphorus oxyacid prepared by a method which comprises adding a phosphorus oxyacid or a derivative thereof capable of releasing a phosphorus oxyacid under the reaction conditions, to a solution of a zirconium concentrate such as zircon sand (ZrO SiO and baddeleyite in a mineral acid such as sulfuric acid, hydrochloric acid and nitric acid, thereby forming a gel composed mainly of a zirconium salt of a phosphorus oxyacid and removing metallic impurities from the gel by extrac tion.
• a zirconium concentrate such as zircon sand (ZrO SiO and baddeleyite in a mineral acid such as sulfuric acid, hydrochloric acid and nitric acid
• the titanium or zirconium salt of a phosphorus oxyacid to be used in the present invention has such a purity that mineral acid ions such as S0,", Cl and N will not be detected by qualitative analysis in the liquor used for water-washing said salt.
• mineral acid ions such as S0,", Cl and N will not be detected by qualitative analysis in the liquor used for water-washing said salt.
• mineral acid ions remain in the titanium or zirconium salt of a phosphorus oxyacid, even if a mixture of carbon and said salt is heated in a nonoxidizing atmosphere or said salt is heated in the absence of carbon in a carbon monoxide atmosphere, there is a tendency that a minute or small amount of the phosphorus oxyacid component remains in the titanium or zirconium component residue.
• mineral acid ions are substantially removed from a titanium or zirconium salt of a phosphorus oxyacid to such an extent that in the liquor used for water-washing said salt mineral acid ions cannot be detected by qualitative analysis, namely, to such an extent that the content of such mineral acid ions is, for instance, less than 100 ppm, especially less than l0 p.p.m.
• the titanium or zirconium salt of a phosphorus oxyacid may be used as it is prepared by the above methods. It is also possible to use a titanium or zirconium salt of a phosphoric oxyacid from which a part of the phosphorus oxyacid component has been removed by subjecting the titanium or zirconium salt ofa phosphorus oxyacid prepared by the above methods to a washing treatment with an alkaline aqueous solution.
• the titanium or zirconium salt of a phosphorus oxyacid may be used in any form of a hydrogel, a dired gel, or a crystalline product obtained by calcining such gel.
• the titanium or zirconium salt of a phosphorus oxyacid is heated at a temperature exceeding 900 C., either in the form of a mixture with carbon in a nonoxidizing atmosphere, or in the absence of carbon in a carbon monoxide atmosphere.
• the phosphorus oxyacid component can be separated as pure phosphorus vapor and the titanium or zirconium component can be recovered as solid residue ofa metal or an oxide.
• any of coke, carbon black, active carbon and pitch may be used as carbon in the present invention.
• purified carbon particularly carbon not containing impurities such as Fe, Mn, V and Cr. From this viewpoint, the use ofcarbon black is most preferred.
• the carbon is used in an amount more than the equimolar amount to the phosphorus oxyacid component (P 0 contained in the titanium or zirconium salt ofa phosphorus oxyacid. More specifically, it is preferred to use carbon in an amount of at least 5 moles, especially ranging from 5 to 10 moles, per mole of the phosphorus oxyacid component expressed as P 0.
• carbon and a titanium or zirconium salt of a phosphorus oxyacid is homogeneously mixed together. In this mixing, in case both starting materials are solid, a homogeneous mixture of them may be prepared by mixing and grinding them by a dry method.
• a homogeneous mixture may be also prepared by wet mixing and grinding both starting materials with the use of a liquid medium, followed by drying. Still further, in case a hydrogel of a titanium or zirconium salt of a phosphorus oxyacid is used, a homogeneous mixture may be prepared by kneading the hydrogel with carbon to form a pastelike mixture and drying the same. In any case, such mixture may be beforehand molded to small masses of an optional form, such as pellet, flake, plate, sphere or tablet. The use of a mixture which has been molded into such small masses is especially preferred, because it results in efficient generation and separation of phosphorus vapor.
• a mixture prepared by adding carbon before the formation of a gel of a titanium or zirconium salt of a phosphorus oxyacid from a titanium or zirconium salt and a phosphorus oxyacid or its derivative, or be fore the molding of a sol or gel of a titanium or zirconium salt of a phosphorus oxyacid into small masses, and washing the resultant mixture with an acid and water, may be applied to the reaction.
• a mixture ofcarbon and a titanium or zirconium salt of a phosphorus oxyacid is heated at a temperature exceeding 900 C. in a nonoxidizing atmosphere.
• the preferable heating temperature range varies depending on the class of the starting salt, but generally speaking, a range of 900l,l00 C. is preferred.
• a range of 900-l ,O50 C. is especially preferred, and in the case of the titanium salt, a range of 930l,l00 C. is especially preferred.
• the nonoxidizing atmosphere there may be used many optional gas as far as it is nonoxidizing and inert to phosphorus, particularly preferred nonoxidizing atmospheres are, carbon monoxide, nitrogen, argon and the like.
• the above mentioned titanium or zirconium salt of a phosphorus oxyacid is heated in the absence of carbon in a carbon monoxide atmosphere.
• the titanium or zirconium salt of a phosphorus oxyacid can be separated into phosphorus and an oxide of titanium or zirconium by heating it in the presence of carbon.
• industrially available carbon such as coke, carbon black and active carbon frequently contains impurities such as iron and silicon, and there is a tendency that the resulting oxide of titanium or zirconium is contaminated with such impurities.
• the separation of phosphorus and titanium or zirconium oxide may be performed by employing only carbon monoxide gas without using carbon. Accordingly, no contamination of the resulting oxide of titanium or zirconium is caused to occur.
• carbon monoxide there may be used not only pure carbon monoxide but also an industrial gas containing carbon monoxide. For instance, city gas, producer gas and the like may be used. But, in view of the fact that phosphorus is separated in the vapor form, it is preferred to use a gas not containing hydrogen.
• the pressure of carbon monoxide to be used is generally not critical, and it may be either atmospheric or superatmospheric.
• a titanium or zirconium salt of a phosphorus oxyacid is heated at a temperature exceeding 900 C. in a carbon monoxide atmosphere.
• the preferable heating temperature range varies depending on the class of the starting salt. Generally, the preferable heating temperature is within a range of from 900 to 1,l00 C. In the case of the zirconium salt, a range of from 900 to l,050 C. is especially preferred, and in the case of the titanium salt, a range of from 930 to 1 100 C. is especially preferred.
• the titanium or zirconium salt of a phosphorus oxyacid is reduced, and hence, the phosphorus oxyacid component is formed into phosphorus vapor and the titanium or zirconium component is left in the form ofa metal or an oxide. Accordingly, it is possible to recover phosphorus vapor and a solid residue of zirconium or titanium by customary known recovery procedures.
• the reactor there may be used a crucible, a furnace, a heating furnace ofa fixed bed type, a moving bed type or a fluidized bed type, or a conventional batchwise or continuous heating furnace such as a rotary kiln, a Herreschoff furnace and a flash roaster.
• the resulting phosphorus vapor may be either used for the preparation of various phosphorus compounds as it is, or recovered as white, yellow or red phosphorus by cooling the vapor with an optional cooling medium.
• the phosphorus vapor in view of the safety it is preferred to recover it in the form of red'phosphorus in a customary known manner.
• the phosphorus vapor is introduced into a recovering device or vessel maintained at approximately 260 C. to 420 C. and is condensed in the form of red phosphorus.
• Titanium or zirconium recovered as solid residue is in the oxide form. Sometimes, a greater portion of titanium or zirconium takes an oxide form but an extremely small portion takes a form ofa metal or a suboxide. Accordingly, the resulting titanium or zirconium residue is converted to white titanium oxide or zirconium oxide after calcination either as it is recovered or optionally after water-washing. The resulting titanium oxide already exhibits a rutile-type crystal structure. However, in order to develop crystals of such titanium oxide, it is preferred to further calcine it at a temperature exceeding 800 C. in an oxygen atmosphere.
• the so obtained titanium oxide or zirconium oxide is substantially free from the phosphoric component and is extremely excellent over known titanium oxides and zirconium oxides with respect to whiteness, particularly reflectivity in the ultraviolet zone. Further, it is substantially free from metallic impurities.
• the titanium oxide or zirconium oxide obtained in accordance with the method of the present invention consists of fine spherical particles substantially free from coagulated particles. Accordingly, such particles exhibit a hiding power comparable to, or higher than, that of a commercially available titanium oxide or zirconium oxide, even when they are not finely pulverized.
• the present invention can enjoy an advantage that the phosphorus oxyacid component in a titanium or zirconium salt of a phosphorus oxyacid can be recovered in the form of pure phosphorus which is of the greatest industrial utility value.
• EXAMPLE I This example illustrates a method of treatment of titanium phosphate wherein purified titanium phosphate prepared used as the starting phosphoric acid component.
• a sulfuric acid solution of titanium salt which is obtained by mixing iron sand slag (produced in Aomori Prefecture, Japan) powder with concentrated sulfuric acid and water, reacting the mixture by heating and thereafter recovering the intended sulfuric acid solution of titanium salt by separating the unreacted materials and gypsum formed; the composition of the solution beingasfollows:
• the so obtained mass is packed in a washing tower and is acid-washed with two types of acid solutions, one a sulfuric acid solution of pH 0.5 and another a sulfuric acid solution of 30 grams per ml. concentration, and removing by extraction and washing the impure metallic constituents such as iron, aluminum and vanadium contained in the hydrogel. This is followed by water-washing until the presence in the washing water of the sulfate group is no longer noted qualitatively, thus obtaining small masses of the hydrogel of titanium phosphate containing substantially no impure metallic constituents.
• the hydrogel of titanium phosphate in which the phosphorus component and titanium component have been readily fixed and separated from the impure metallic constituents is molded into pellets of columnar form of diameter about l.5 mm. and length about 5-15 mm. using a extruding granulator and thereafter dried thoroughly at 1 10 C.
• the dried product of columnar particulate form is charged to a reaction tube of a reaction apparatus and reacted by heating in carbon monoxide.
• the reaction apparatus used is made up of a reaction tube and a phosphorus recovery apparatus.
• the reaction tube which comprises a quartz glass tube 55 cm. long and 3 cm. in diameter is-used vertically. Thirty cm. of its middle portion is placed in an electric furnace which is capable of heating the tube up l,2001,20' C. in its bottom part a gaseous atmosphere of carbon monoxide is maintained.
• the bottom is provided with an entry port from which carbon monoxide is introduced, which becomes the carrier gas for the phosphorus vapor formed.
• a discharge port is provided at the top for the carrier gas and the phosphorus vapor formed.
• Heat-resistant porcelain balls 3 mm. in diameter are packed in the bottom part of the reaction tube so as to make possible the placement of the hereinabove prepared dried titanium phosphate of columnar particulate form at the middle portion (30 cm.) of the reaction tube, after which about 20 grams of the dried product is so placed above the packed balls.
• a Pyrex glass tube 300 cm. long and 2 cm. in diameter is used as the phosphorus recovery apparatus.
• This glass tube is packed with porcelain balls 2 mm. in diameter, and provisions are made so as to enable the glass tube to be heated and maintained at a temperature of 360 1- C., by means of an air bath.
• This phosphorus recovery apparatus is connected to the discharge port of the reaction tube, from whence the phosphorus vapor formed therein is conducted along with the carrier gas into the recovery apparatus maintained at 360 i 5 C. where the phosphorus vapor is condensed on the porcelain balls as red phosphorus.
• the carbon monoxide used which is introduced from the entry port at the bottom of the reaction tube, is used for maintaining the reducing atmosphere as well as cycled and used as the carrier gas for the phosphorus vapor formed.
• the rate of flow of the gas at this time is held to a rate of about one liter per minute.
• the porcelain balls on which has been condensed the red phosphorus which can be safely touched with hand are taken out, and using porcelain balls themselves as the comminution medium the wet comminution of the red phosphorus is carried out in customary manner followed by drying, whereupon powdery red phosphorus is recovered.
• the porcelain balls from which the red phosphorus has been removed are again packed in the phosphorus recovery apparatus to be reused as the packing material.
• titanium phosphate in which the phosphorus and titanium components have been readily fixed and purified is effectively processed by heating and reacting under an atmosphere of carbon monoxide to readily yield red phosphorus and rutile of high utility value.
• This examples illustrates a method of treatment of zirconium phosphate wherein purified zirconium phosphate prepared using as starting materials crude phosphoric acid and a solution of a crude zirconium salt is heated in an atmosphere of carbon monoxide to recover the phosphorus formed at this time as red phosphorus while, on the other hand, recover the zirconium component as zirconium oxide.
• crude phosphoric acid (54.5 percent as P 0 is used.
• zirconium component As the starting zirconium component is used a sulfuric acid solution of zirconium salt, which is obtained by acid decomposing zirconium sand (zircon) and separating the silicic acid component and unreacted reactants by filtration to recover the foregoing solution having the following composition:
• Free H 50 l LS 230 Grams of the foregoing crude phosphoric acid is stirred with a commercial mixer (2,000 rpm.) at room temperature. To this is then added at once one kg. of the recovered sulfuric acid solution of zirconium salt with stirring to thus obtain a pasty gel predominantly of zirconium phosphate.
• This pasty gel is separated from the motherliquor using Buchner.s filtration apparatus to render it into a cakelike gel, after which the impure metallic constituents, such as iron and aluminum, continued in the cakelike gel are removed by washing, this being accomplished by acid-washing the cake with a sulfuric acid solution of 20 grams per 100 ml. concentration.
• the prepared hydrogel of zirconium phosphate is molded into pellets of columnar form about 5-1 5 mm. long and about 1.5 mm. in diameter, using an extruder type pelleter, and thereafter dried thoroughly at 1 C.
• EXAMPLE 3 This example illustrates a method of recovering the phosphorus and titanium components by the heat treatment in an atmosphere of carbon monoxide the titanium salts of phosphorus oxyacids prepared using the various phosphorus oxyacids or their derivatives.
• the starting titanium component is used a sulfuric acid solution of titanium salt obtained by adding water and concentrated sulfuric acid to finely divided ilmenite ore, reacting this mixture by heating, recovering the sulfuric acid solution of titanium salt from the resulting gruellike reaction product by extraction with water, and thereafterseparating by cooling and crystallizing the iron sulfate which has become dissolved in the sulfuric acid solution at the same time in this case.
• the sulfuric acid solution of titanium salt recovered hereinabove has the following composition:
• the starting phosphoric acid component the various commercially available reagent phosphorus oxyacids or their derivatives as well as ore are used.
• the phosphorus ore produced in Kola, U.S.S.R., after being thoroughly wet-ground, submission to elutriation and magnetically removed of part of its iron, is used. its principal constituents are P 0 38.86 wt. percent, CaO 51.39 wt. percent, Fe O A1 0 0.48 wt. percent, Na O K 0 0.29 wt. percent, SiO 1.02 wt. percentand F 3.36 wt. percent.
• sulfuric acid in at least an equimolar quantity of the various oxyacid salts is added in advance to the sulfuric acid solution of titanium salt.
• composition molecular weight ratio composition
• amount of impurities contained of the various purified titanium salt of phosphorus oxyacids are shown in Table III.
• the resulting titanium salts of phosphorus oxyacids do not contain any impure metallic constituents such as vanadium, iron, arsenic and fluorine regardless of the class of the phosphorus oxyacid used.
• the amount of impurities contained shown in Table iii are the results of having conducted the identification of the impure metallic constituents contained, using an emission spectrophotometer.
• the sign means that amount was such that it could not be substantially detected with the emission spectrophotometer, the sign (i) denotes that a minute amount was detected, the sign indicates that a pronounced amount was detected, and the sign means that an especially large amount was detected.
• the impurities contained will hereinafter be indicated by these signs.
• the various titanium salts of phosphorus oxyacids, described hereinbefore, are granulated, dried and prepared into dried products having particles of columnar form by operating as in Example 1.
• EXAMPLE 4 This example illustrates a method of heat treatment in an atmosphere of carbon monoxide titanium phosphate prepared varying the TiO :P O mole ratio.
• Example 1 the free sulfuric acid content of a sulfuric acid solution of titanium salt obtained by the acid decomposition of iron sand slag is brought to weight percent by adding concentrated sulfuric acid. To 140 grams each of this solution are respectively added 2.1, 3.1, 3.6, 5.1, i5, 24 and ml. of chemically pure reagent orthophosphoric acid, which solution are then formed into homogeneous liquid mixtures. Titanium phosphate gels of varying TiO :P O,, mole ratios and not containing substantially any impure metallic constituents are prepared from the foregoing liquid mixtures.
• titanium phosphate gel prepared by adding 5.1 ml. of orthophosphoric acid is also adjusted as to its mole ratio by partial dephosphatizing with ammonia water.
• the titanium phosphates which have been prepared as hereinbefore described with varying TiO :l O mole ratios and wherein the phosphorus and titanium components have been fixed and purified are granulated and dried and prepared into dried products of columnar particulate form by operating as in Example 1.
• Example 1 These several dried products are each charged to a reaction tube of a reaction apparatus such as was used in Example I.
• the phosphorus components of the titanium phosphate of the several mole ratios become phosphorus vapors, which are conducted by means of the gas used as the atmosphere acting as a carrier gas to a phosphorus recovery apparatus and condense as red phosphorus on the porcelain balls of the recovery apparatus maintained at 360i5 C.
• the here formed red phosphorus is recovered as powdery red phosphorus by operating in each case as in Example I.
• Purified phosphorus ore (produ Phospho- Reflectivity, percent rus com- Covering ponent (Wavelength my) power, contained, 350 400 500 600 mm. percent Content of Impurities TABLE IV i Starting Titanium Phosphate Gel Recovered Rutilo Phosphogro l ratitg iContegti of R(evarrietipity, Ipercent rus comcom 05 on o mpur es ave en t m 1 Amount addcd of phosphoric acid at time of preparation, resulting gel g m 5851;? conifiiiii m l.
• EXAMPLE This example illustrates a method of heat treatment of purified gels of titanium phosphate and zirconium phosphate in an atmosphere of carbon monoxide after they have been treated at varying temperatures.
• the gels of either titanium phosphate or zirconium phosphate prepared in accordance with the procedures described in A of Example 1 and A of Example 2 are each treated under the conditions of room temperature (in a desiccator containing a desiccant) X 24 hours, 50 C. X 3 hours, 100 C. X 1 hour, 500 C. X 30 minutes, 800 C. X 30 minutes and 1.000" C. x 30 minutes.
• room temperature in a desiccator containing a desiccant
• titanium phosphates and zirconium phosphates that were treated under these various conditions were analyzed with an X-ray diffraction apparatus, it was found that the titanium phosphate or zirconium phosphate trated at room temperature, 50 C. and 100 C. were non-crystalline, but that when treated ati 500 C., they were partially crystallized, and when treated at. 800 C. and 1,000 C., they were completely crystalline.
• Water is added to the titanium or zirconium phosphate that has been treated under different conditions in amounts of 50-60 weight percent thereof. With this water as the blending medium and by operating as in Example 1, the several phosphates are each granulated and made into dried products of form of small masses or columnar particulate form.
• reaction tube of a reaction apparatus such as was used in Ex- 5 EXAMPLE 6 ample 1 and are maintained for about 90 minutes at 950- l,000 C. as in Examples 1 and 2 using carbon monoxide, the phosphorus component which had been contained in the starting material as titanium or zirconium phosphate becomes phosphorus vapor which is conducted into the phosphorus recovery apparatus by means of the gas which was used as the atmosphere acting as a carrier gas to become condensed as red phosphorus on the porcelain balls of the recovery ap; paratus.
• the red phosphorus formed in each case is recovered as powdery red phosphorus by operating as in Example
• This example illustrates a method of treatment of titanium phosphate wherein a carbon-incorporated titanium phosphate gel prepared from crude phosphoric acid, crude titanium salt As the starting phosphoric acid component, 54.5 percent (P,O,) crude phosphoric acid is used. On the other hand, the 6.07 percent (TiO crude titanium salt solution recovered from iron slag, as in A of Example 1, is used as the titanium component.
• hydrogel of titanium phosphate is slurried into a pasty state by stirring with a commercial mixer (2,000 r.p.m.) after which a carbon black powder commercially available as acetylene black is added to the slurry in an amount of 20 weight parts per 100 weight parts of the dry titanium phosphate followed by stirring with the mixer to obtain a pasty slurry of carbon-incorporated titanium phosphate.
• a carbon black powder commercially available as acetylene black
• hydrogel of carbon-incorporated titanium phosphate is molded into pellets of columnar form about 1.5 mm. in diameter and about 5-15 mm. long, using an extrusion granulator (pelleter type) followed by thorough drying.
• EXAMPLE 7 This example illustrates a method wherein a mixed gel of titanium phosphate and zirconium phosphate is, after blending, heat treated in an atmosphere of carbon dioxide.
• phosphoric acid component is chosen commercially available chemically pure reagent phosphoric acid (85 percent, sp. gr. 1.69).
• titanium component is chosen commercially available chemically pure reagent titanium tetrachloride dilutedby hydrochloric acid solution such that the content therein of the titanium component (calculated as Tiog) is 10.0 grams per 100 ml. 100 Grams of crystals of commercially available chemically pure reagent zirconium nitrate [ZrNO -SH O], are added to 200 ml. of the foregoing titanium tetrachloride solution and dissolved homogeneously therein, after which 37 ml.
• H PO percent phosphoric acid
• the so obtained pasty gel mixture of titanium phosphate and zirconium phosphate gels is extracted and removed of the impure metallic constituents it contains by using sulfuric acid solution of a concentration of 20 grams per mi. and thereafter water-washed to obtain a mixed gel of titanium phosphate and zirconium phosphate containing substantially no impure metallic constituents.
• this mixed gel did not contain any vanadium, iron, arsenic, fluorine, aluminum or chromium.
• Example 6 After purifying the foregoing mixed gel of titanium and zirconium with hydrochloric acid, the powdered carbon black used in Example 6 is added thereto in an amount 20-30 percent in excess of the chemical reaction equivalent, based on the phosphoric acid component (P 0 contained in the mixed gel, followed by thorough mixing of the two components with a commercial mixer to thus obtain a black mixed gel containing carbon.
• This carbon-incorporated mixed gel is molded as in Example 6 into columnar pellets having a diameter of about 1.5 mm., followed by drying to obtain dried carbon-incorporated titanium phosphate pellets of columnar form.
• the carbon-incorporated mixed gel prepared as described hereinbefore is charged to a reaction tube of a reaction apparatus such as was used in Example 1 and is held for about 60 minutes at 950-1 ,000C., using carbon monoxide as the gaseous atmosphere, whereupon the phosphorous component becomes phosphorus vapor and is conducted by means of the gas of the atmosphere acting as a carrier gas into the phosphorus recovery apparatus, where it condenses as red phosphorus on the porcelain balls of the recovery apparatus maintained at 360+ C.
• the so formed red phosphorus is recovered as powdery red phosphorus by operating as in Example 1.
• the residue containing the unreacted carbon which remains in the reaction tube after the completion of the reaction, is calcined at 800 C. in an oxygen atmosphere.
• the so obtained white calcined product is analyzed for its crystal structure by means of X-rays it was confirmed to be a mixture of rutile and zirconia.
• observations of the particles of the white calcined product were made with an electron microscope, it was observed that the surface of the rutile of particle diameter about 0.1-0.5 micron was coated with about 0.08-0.02 micron of zirconium dioxide.
• argon Ar
• nitrogen N a gas mixture (about M by volume) of carbon dioxide (C0,) and carbon monoxide (CO)
• a gas mixture about 1:1 by volume of nitrogen (N and carbon monoxide (CO).
• P-Ti R as. 0 99. 0 100. 5 100. 5 D0.
• P-Zr Z 85.0 103.0 103.0 103. 5 Added- P-Ti R 18.0 65.0 98.0 98. 5 ..d0 -Zr Z 78. 5 08.0 104.0 104.0 I P-T: titanium phosphate; P-Z: zirconium phosphate; R: rutile; Z: zirconia.
• EXAMPLE 9 88 $3: This example illustrates a method of effectively treating 500 102:0 titanium phosphate by mixing various classes of carbon in a 600 102.5 purified titanium phosphate gel and heating the mixtures in an EXAMPLE 8 This example illustrates the instance where heat treatment is carried out in a variety of nonoxidizing gaseous atmospheres, using either the purified titanium phosphate gel or zirconium phosphate alone or with the incorporation in these gels of carbon.
• the purified titanium phosphate gel As the purified titanium phosphate gel, the gel obtained in accordance with the procedure described in A of Example 1 is used, while as the purified zirconium phosphate gel, that obtained as described in A of Example 2 is used, which gels are then prepared into the dried gels of columnar particulate form in accordance with the method described in Examples 1 and 2.
• the respective dried carbon-incorporated gels are prepared as in Example 7 by mixing the carbon black powder in either the purified titanium phosphate gel of zirconium phosphate gel obtained in accordance with Examples 1 and 2, molding the mixtures into pellets of columnar form and thereafter drying the gels.
• the purified titanium phosphate gel and the four classes of finely divided carbon are mixed and each of the mixtures are made into dried pellets of columnar form by operating as in Example 7.
• phosphorus component turns into phosphorus vapor while a pan of the titanium component is converted into metallic titanium when a mixture of purified titanium phosphate gel and carbon is reduced by heating in a nonoxidizing atmosphere of argon.
• the purified carbon-incorporated titanium phosphate As the purified carbon-incorporated titanium phosphate, the mixed gel prepared as in Example 6 and containing 30 weight parts per 100 weight parts of the phosphate, of carbon black is used. This is granulated and dried and made into a dried product ofcolumnar particulate form.
• the vertical type reaction apparatus such as was used in Example I is used. except that the method of introducing the nonoxidizing gaseous atmosphere has been changed. instead of flowing the gas upwardly from the bottom, it is flowed downwardly from the top, i.c., the inlet port is provided at the top of the reaction tube, and the gas discharge port is provided at the bottom.
• the setup is such that the red phosphorus is recovered by conducting the forming phosphorus vapor from the discharge outlet port at the bottom of the reaction tube to a phosphorus recovery apparatus such as was described in Example 1 my means of the gas ofthe nonoxidizing atmosphere acting as the carrier gas.
• EXAMPLE 10 This example illustrates the method of recovering yellow. phosphorus by treating either purified titanium phosphate gel or zirconium phosphate gel in the presence of carbon monoxide.
• the purified titanium phosphate gel and zirconium phosphate gel As the purified titanium phosphate gel and zirconium phosphate gel, the gels prepared by the procedures described in A of Example 1 and A ofExample 2, respectively, are used.
• yellow phosphorus and an oxide of either titanium or zirconium excelling in whiteness can be obtained by heat treating the purified phosphates of either titanium or zirconium in an atmosphere ofcarbon monoxide.
• EXAMPLE l1 This example illustrates a method of treating titanium 40 FfiitiihEtitanium.
• argon (Ar) is flowed into this apparatus as the nonoxidizing gas atmosphere, at the rate of one liter per minute, and the temperature of the reaction tube is raised.
• the reaction is carried out for 5 hours at 950l ,0OO C.
• the phosphorus vapor formed is recovered as red phosphorus and a part of the titanium component is reduced to metallic titanium and condenses on the wire network of metallic titanium suspended in the upper part of the reaction tube. Furthermore, condensation of metallic titanium having a dark gray metallic luster also takes place on the wall of the reaction tube.
• M is a titanium or zirconium atom, with 5 to mols, per mol of the phosphorus oxyacid component (P 0 in said salt, of carbon; heating the resultant mixture at a temperature of about from 950 C. to 1,000 C. in a nonoxidizing atmosphere; separating the vapor of phosphorus generated; thereafter, calcining the obtained solid residue in an oxygen atmosphere at a temperature not lower than 500 C.; and recovering the titanium oxide or zirconium oxide formed.
• a process for treating a titanium or zirconium salt of a phosphorus oxyacid which comprises heating a titanium or zirconium salt of a phosphorus oxyacid having the following composition expressed as the oxide 7 at a temperature of about 950 C. to 1,000 C. in the absence of carbon in an atmosphere of carbon monoxide; separating the vapor of phosphorus generated; thereafter, calcining the solid residue obtained in an oxygen atmosphere at a temperature not lower than 500 C.; and recovering the titanium oxide or zirconium oxide formed.

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  • 1969-08-05 SE SE10920/69A patent/SE350469B/xx unknown
  • 1969-08-05 US US847633A patent/US3650681A/en not_active Expired - Lifetime
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